US5478917A - Solutions of polyimide-forming substances and their use as coating compositions - Google Patents
Solutions of polyimide-forming substances and their use as coating compositions Download PDFInfo
- Publication number
- US5478917A US5478917A US08/320,396 US32039694A US5478917A US 5478917 A US5478917 A US 5478917A US 32039694 A US32039694 A US 32039694A US 5478917 A US5478917 A US 5478917A
- Authority
- US
- United States
- Prior art keywords
- acid
- solutions
- bis
- diaminodiphenyl
- polyimide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31721—Of polyimide
Definitions
- the present invention relates to solutions of polyimide-forming substances, containing
- the present invention furthermore relates to the use of such solutions for the production of coatings and of articles coated with polyimides, and coated articles.
- Aromatic polyimides are as a rule insoluble in conventional organic solvents. In general, solutions of the more readily soluble polyamidocarboxylic acids were therefore used as polyimide-forming intermediates for polyimide-forming coatings. The polyimides then form from these intermediates on drying, for which temperatures of up to 400° C. are used.
- polyamidocarboxylic acids have a short shelf life since they tend to undergo self-hydrolysis and premature imide formation. Most polyamidocarboxylic acid coating materials therefore have to be stored in a freezer.
- U.S. Pat. No. 3,700,649 discloses polyimides which are obtained from aromatic diamines and symmetric diesters of benzophenonetetracarboxylic acid.
- U.S. Pat. No. 3,347,808 discloses solutions of polyamines and alkyl esters of tetracarboxylic acids.
- U.S. Pat. No. 4,874,835 relates to mixtures of special diamines with oxydiphthalates.
- polyimides are polyimides, but polyheterocycles such as polyisoindoloquinazolinediones or polyarylenebenzimidazoles are also included.
- polyimide is used below as a synonym for all polyheterocycles.
- Preferred polyamine components A) are aromatic and/or partly aromatic polyamines, diamines being preferred.
- Suitable diamines are:
- alkylisopropyltoluylenediamines such as diisopropyltoluylenediamine
- polyamines are tetraamines, such as 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenylmethane, 3,3',4,4'-tetraaminodiphenyl ether, 3,3',4,4'-tetraaminodiphenyl sulfone or 3,3',4,4'-tetraaminodiphenyl sulfide.
- tetraamines give polyarylenebenzindazoles as the final structure.
- a further important group of diamines comprises aromatic polynuclear compounds which are bonded via benzanilide groups, eg. 3,3'-diaminobenzanilide, 3,4'-diaminobenzanilide, 4,3'-diaminobenzanilide, 4,4'-diaminobenzanilide or 4,3'-diaminobenzanilide, and the N-alkyl substitution products of these anilides, as well as the ⁇ , ⁇ -diaminopolyanilides according to EP-A 271736.
- benzanilide groups eg. 3,3'-diaminobenzanilide, 3,4'-diaminobenzanilide, 4,3'-diaminobenzanilide, 4,4'-diaminobenzanilide or 4,3'-diaminobenzanilide, and the N-alkyl substitution products of these anilides, as well as the ⁇ , ⁇ -dia
- the object is to obtain polyimides having the best possible combinations of properties. These are obtained by means of a wholly aromatic structure.
- the novel polyimides are therefore preferably prepared using purely aromatic diamines.
- dimmines which are not purely aromatic generally have an adverse effect on the heat stability of the end products
- cycloaliphatic, heterocyclic and aliphatic amine compounds having an amine functionality greater than 1, preferably 2 or higher, may however be used or be present for obtaining specific properties, such as surface smoothness, flexibility, etc.
- diamino(dimethyl)dicyclohexylmethane diamino(dimethyldiisopropyl)dicyclohexylmethane, diamino(tetraisopropyl)dicyclohexylmethane, diamino(diisopropyl)dicyclohexylmethane, diaminoalkylenes or diaminopolyoxyalkylenes.
- dimmines is intended to include compounds which contain the structural element N--N, ie. derivatives of hydrazine.
- Aromatic dimmines which are further substituted by reactive groups in the nucleus are also important.
- Such reactive substituents are, for example, carboxyl, hydroxyl, amine and amide groups.
- polyheterocycles having a nonimide structure are then also formed.
- polyisoindoloquinazolinediones are obtained as the final structure.
- Polybenzoxazoles are obtained using dihydroxydiamines, and polyarylenebenzimidazoles using tetraamines. The present invention also relates to such polymers.
- salts and partial salts of the amines may also be used or may be present, for example the carbonates, acetates, trifluoroacetates, trichloroacetates, formates, oxalates, maleates, methanesulfonates, benzenesulfonates, chlorides, etc. It has been found that the use of such salts suppresses the strong discoloration, particularly of the aromatic diamines, and gives smoother films in the case of some combinations.
- Suitable components B) are amides or mixtures of esters and amides of tetracarboxylic acids.
- tetracarboxylic acid derivatives may be described by the general formula I: ##STR1##
- X may be --O--, --NH-- or --NR 1 --.
- Z is a tetravalent, aromatic or partly aromatic radical which may furthermore be modified by a heterocyclic structure, or may furthermore be an aliphatic or cycloaliphatic radical which may also comprise partially or completely halogenated structural elements.
- R 1 is alkyl having 1 to 20 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl or heptyl or an isomer thereof, octyl, 2-ethylhexyl or another higher homolog, or cycloalkyl, preferably cyclohexyl or methylcyclohexyl, alkoxyphenyl, preferably phenoxybutyl, phenoxypropyl or phenoxyethyl, aryl such as phenyl, benzyl, cumyl or cresyl, or hydrogen.
- R 1 is particularly preferably ethyl, propyl, isopropyl, n-butyl or one of the stated alkoxyphenyl radicals.
- Diamides or diesters are preferred, ie. R 1 may simultaneously be hydrogen and the other stated radicals.
- the diamides or diesters may be symmetric or asymmetric.
- Y is --O--, --NH-- or --NR--, where --R-- has the same meanings as R 2 .
- R 2 is a divalent alkyl or alkoxyalkyl radical of 2 to 6 carbon atoms.
- tetracarboxylic acids are suitable parent tetracarboxylic acids from which the radical Z is derived.
- Aromatic or partly aromatic tetracarboxylic acids such as
- Butane-1,2,3,4-tetracarboxylic acid, cyclobutanetetracarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, pyrrolidine-2,3,4,5-tetracarboxylic acid, thiophene-2,3,4,5-tetracarboxylic acid, pyrazine-2,3,5,6-tetracarboxylic acid, tetrahydrofurantetracarboxylic acid, 9-bromo-10-mercaptoanthracenetetracarboxylic acid, 9,10-dimercaptoanthracenedicarboxylic acid, 2,6-endovinylenecyclohexane-1,2,4,5-tetracarboxylic acid and hexafluoroisopropylidene-2,2-bis(phthalic anhydride) are also suitable.
- Suitable isomers and substitution products of the stated polycarboxylic acids are halogen-substituted products, in particular fluorine-substituted or perfluoro products and/or alkyl-substituted products and polycarboxylic acids containing silicon.
- the dimerization and oligomerization products of trimellitic anhydride with alcohols, amines and isocyanates having a functionality of >2 and especially the 4,4-esterification, 4,4-etherification and 4,4-amidation dimers of trimellitic acid are also suitable.
- the salts or partial salts of tetracarboxylic acid compounds may also be used or may be present, provided that they still have free carboxyl groups, for example ammonium salts and salts with readily volatile amines, such as mono-, di- and trimethylamine, mono-, di- and triethylamine and other amines.
- the phosphonium and sulfonium salts of acidic tetracarboxylic acid compounds may also be used or may be present. The use of such salts generally leads to desired, lower viscosities in conjunction with a higher solids content.
- tetracarboxylic acids stated are known or can be prepared by known processes.
- the tetracarboxamides and tetracarboxylic esters can be prepared in a known manner by reacting the corresponding tetracarboxylic dianhydrides with primary and/or secondary monoamines and monoalcohols (compounds I) or with primary and/or secondary diamines or diols (compounds of the formula II).
- Diamides and diesters are preferably prepared by using corresponding molar amounts of amine/alcohol.
- the mono, tri or tetra derivatives or mixtures thereof with the diamides or diesters can also be prepared by using correspondingly larger or smaller amounts of amine/alcohol, and can be used.
- the manner in which the reaction can be appropriately controlled is known to a person skilled in the art.
- the amides or esters can be prepared separately or alongside one another. It is also possible concomitantly to use relatively small amounts of water or not to remove all the resulting water of reaction, so that free tetracarboxylic acids can be obtained, also in proportions.
- amides or ester/amide mixtures are used as components B).
- the amount of amide may be from 20 to 80, preferably from 40 to 60, mol %.
- novel intermediates are as a rule synthesized in suitable organic solvents; preferred substances are polar substances, such as:
- dialkylacetamides such as
- alkylalkylenediureas such as
- alkyleneureas such as
- N-alkylpyrrolidones such as
- NMP N-methylpyrrolidone
- polar substances may be partially or completely replaced by further solvents, such as alcohols, esters, ketones, ethers and cycloaliphatic ketones, alcohols, esters, amines, especially tertiary amines, such as triethylamine, water, glycols, glycol esters, glycol ethers and hydrocarbons.
- solvents such as alcohols, esters, ketones, ethers and cycloaliphatic ketones, alcohols, esters, amines, especially tertiary amines, such as triethylamine, water, glycols, glycol esters, glycol ethers and hydrocarbons.
- solvents such as alcohols, esters, ketones, ethers and cycloaliphatic ketones, alcohols, esters, amines, especially tertiary amines, such as triethylamine, water, glycols, glycol esters, glycol ethers and hydrocarbons.
- the choice of solvent depends on the so
- novel solutions contain the polyamine A) and the tetracarboxylic acid derivatives B) preferably in a molar ratio of from 1.5:1 to 1:1.5, particularly preferably 1:1.
- the solids content of the solutions is preferably from 35 to 60% by weight.
- the viscosity is preferably from 500 to 10,000 mPa.s. For specific applications, however, the desired parameters may be adjusted as required by corresponding dilution.
- tetracarboxylic acid derivatives, polyamine and solvent may be combined in any order.
- stirring is carried out, if required, at room temperature or at elevated temperatures, for example from 30° to 120° C., in particular 40°-80° C.
- novel solutions may contain conventional additives, such as catalysts for imide formation, dyes, pigments, fillers, leveling agents and viscosity regulators.
- the coating is preferably cured at final temperatures of from 150° to 450° C., particularly preferably from 300° to 400° C. It has proven particularly advantageous to carry out the curing process in a plurality of stages by gradually increasing the temperature to the final temperature.
- novel solutions are used in the coating of silicon wafers for producing electronic circuits, ceramic and metal for producing composite circuits, in particular for the production of multi-chip modules, for coating wire, for coating optical waveguides of glass or quartz, for coating metal films for the production of flexible printed circuit boards, for coating, impregnating and adhesively bonding ordered and random, sheet-like and formed fiber materials, for encapsulating electronic and electric circuits and windings and for the production of powders, fibers, free films or moldings.
- the tetracarboxylic acid component was first reacted with the amine component and, if required, the alcohol component, after which the diamine component A) was added.
- Comparative Example 1 corresponds to Example 1 of U.S. Pat. No. 3,347,808
- Coating materials from which these polyimides can be obtained are therefore offered by most polyimide producers. They are all relatively dilute solutions of polyamidocarboxylic acids.
- the examples which follow show that it is possible according to the present invention, by using (partial) esters and (partial) amides, also to prepare such polyimides from highly concentrated solutions having a long shelf life.
- Examples VB3, VB4, B2 and B3 show the considerable advance of the novel starting materials with regard to the ratio of viscosity to solids content, the film formation capacity also being excellent.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Paints Or Removers (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4335322.3 | 1993-10-18 | ||
DE4335322A DE4335322A1 (de) | 1993-10-18 | 1993-10-18 | Lösungen polyimidbildender Substanzen und deren Verwendung als Beschichtungszusammensetzungen |
Publications (1)
Publication Number | Publication Date |
---|---|
US5478917A true US5478917A (en) | 1995-12-26 |
Family
ID=6500317
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08/320,396 Expired - Fee Related US5478917A (en) | 1993-10-18 | 1994-10-11 | Solutions of polyimide-forming substances and their use as coating compositions |
Country Status (6)
Country | Link |
---|---|
US (1) | US5478917A (ja) |
EP (1) | EP0648795A1 (ja) |
JP (1) | JPH07179606A (ja) |
KR (1) | KR950011498A (ja) |
CN (1) | CN1106843A (ja) |
DE (1) | DE4335322A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999062989A1 (en) * | 1998-05-29 | 1999-12-09 | The Government Of The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration (Nasa) | Films, preimpregnated tapes and composites made from polyimide 'salt-like' solutions |
US20030144461A1 (en) * | 2001-12-21 | 2003-07-31 | Kaneka Corporation | Manufacturing method of polyamic acid, and polyamic acid solution |
US20030153719A1 (en) * | 2001-12-26 | 2003-08-14 | Takashi Kato | Novel polymer compound, precursor for the same and thin film-forming method using the same polymer precursor |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1301690B1 (it) * | 1998-06-11 | 2000-07-07 | Sinco Ricerche Spa | Miscele di resine poliestere aventi elevate proprieta' di barriera aigas. |
TWI283783B (en) * | 1999-12-09 | 2007-07-11 | Jsr Corp | Liquid crystal alignment film and liquid crystal display device |
JP2007246628A (ja) * | 2006-03-14 | 2007-09-27 | Jsr Corp | 被膜形成用樹脂組成物 |
AU2012305578B2 (en) * | 2011-09-09 | 2016-08-04 | Japan Matex Co., Ltd. | Composite material |
CN109337428A (zh) * | 2018-10-17 | 2019-02-15 | 陕西航空电气有限责任公司 | 一种耐高温聚酰亚胺绝缘浸渍漆及其制备方法和应用 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3347808A (en) * | 1966-07-05 | 1967-10-17 | Monsanto Co | Coating compositions |
US3502712A (en) * | 1966-12-20 | 1970-03-24 | Monsanto Res Corp | Bis(dialkylaminoalkyl) 4,4'-carbonylphthalate |
US3700649A (en) * | 1971-07-06 | 1972-10-24 | Int Harvester Co | Polyimides of benzophenone tetracarboxylic acid esters and aromatic diamines having a basicity constant of less than 10-" and method of preparation |
EP0271736A1 (en) * | 1986-11-20 | 1988-06-22 | Nippon Steel Chemical Co., Ltd. | Resins of low thermal expansivity |
US4874835A (en) * | 1987-09-14 | 1989-10-17 | General Electric Company | Polyetherimides and precursors therefor from oxydiphtalic anhydride diester and a mixture of diamines |
US4960824A (en) * | 1988-09-26 | 1990-10-02 | General Electric Company | Storage stable polyimide precursor solutions and method of preparation |
US5264545A (en) * | 1991-10-24 | 1993-11-23 | Basf Lacke+Farben Aktiengesellschaft | Solutions of polyimide-forming starting materials |
US5332799A (en) * | 1991-10-24 | 1994-07-26 | Basf Lacke+Farben Aktiengesellschaft | Solutions of polyimide-forming starting materials |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5004627A (en) * | 1989-10-10 | 1991-04-02 | Ethyl Corporation | Polyimides for mold release |
-
1993
- 1993-10-18 DE DE4335322A patent/DE4335322A1/de not_active Withdrawn
-
1994
- 1994-09-21 JP JP6226914A patent/JPH07179606A/ja active Pending
- 1994-10-10 EP EP94115931A patent/EP0648795A1/de not_active Withdrawn
- 1994-10-11 US US08/320,396 patent/US5478917A/en not_active Expired - Fee Related
- 1994-10-18 CN CN94112809A patent/CN1106843A/zh active Pending
- 1994-10-18 KR KR1019940026589A patent/KR950011498A/ko not_active Application Discontinuation
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3347808A (en) * | 1966-07-05 | 1967-10-17 | Monsanto Co | Coating compositions |
US3502712A (en) * | 1966-12-20 | 1970-03-24 | Monsanto Res Corp | Bis(dialkylaminoalkyl) 4,4'-carbonylphthalate |
US3700649A (en) * | 1971-07-06 | 1972-10-24 | Int Harvester Co | Polyimides of benzophenone tetracarboxylic acid esters and aromatic diamines having a basicity constant of less than 10-" and method of preparation |
EP0271736A1 (en) * | 1986-11-20 | 1988-06-22 | Nippon Steel Chemical Co., Ltd. | Resins of low thermal expansivity |
US4874835A (en) * | 1987-09-14 | 1989-10-17 | General Electric Company | Polyetherimides and precursors therefor from oxydiphtalic anhydride diester and a mixture of diamines |
US4960824A (en) * | 1988-09-26 | 1990-10-02 | General Electric Company | Storage stable polyimide precursor solutions and method of preparation |
US5264545A (en) * | 1991-10-24 | 1993-11-23 | Basf Lacke+Farben Aktiengesellschaft | Solutions of polyimide-forming starting materials |
US5332799A (en) * | 1991-10-24 | 1994-07-26 | Basf Lacke+Farben Aktiengesellschaft | Solutions of polyimide-forming starting materials |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999062989A1 (en) * | 1998-05-29 | 1999-12-09 | The Government Of The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration (Nasa) | Films, preimpregnated tapes and composites made from polyimide 'salt-like' solutions |
US6222007B1 (en) | 1998-05-29 | 2001-04-24 | The United States Of America As Represented By The National Aeronautics And Space Administration | Films, preimpregnated tapes and composites made from polyimide “Salt-like” Solutions |
US20030144461A1 (en) * | 2001-12-21 | 2003-07-31 | Kaneka Corporation | Manufacturing method of polyamic acid, and polyamic acid solution |
US6852826B2 (en) * | 2001-12-21 | 2005-02-08 | Kanera Corporation | Manufacturing method of polyamic acid, and polyamic acid solution |
US20030153719A1 (en) * | 2001-12-26 | 2003-08-14 | Takashi Kato | Novel polymer compound, precursor for the same and thin film-forming method using the same polymer precursor |
US6949618B2 (en) * | 2001-12-26 | 2005-09-27 | Chisso Corporation | Polymer compound, precursor for the same and thin film-forming method using the same polymer precursor |
Also Published As
Publication number | Publication date |
---|---|
KR950011498A (ko) | 1995-05-15 |
EP0648795A1 (de) | 1995-04-19 |
CN1106843A (zh) | 1995-08-16 |
DE4335322A1 (de) | 1995-04-20 |
JPH07179606A (ja) | 1995-07-18 |
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Owner name: BASF LACKE + FARBEN AKTIENGESELLSCHAFT, GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BLUM, RAINER;HOFFMANN, GERHARD;REEL/FRAME:007182/0213 Effective date: 19941006 |
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Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |
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Effective date: 20031226 |